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Publication Detail
The Role of Photoisomerisation on the Photodetachment of the Photoactive Yellow Protein Chromophore.
The photocycle of photoactive yellow protein (PYP) is initiated by a photoinduced trans-cis isomerisation around a C=C bond in the chromophore that lies at the heart of the protein; however, in addition to the desired photochemical pathway, the chromophore can undergo competing electronic relaxation processes. Here, we combine gas-phase anion photoelectron spectroscopy and quantum chemistry calculations to investigate how locking the C=C bond in the chromophore controls the competition between these electronic relaxation processes following photoexcitation in the range 400-310 nm. We find evidence to suggest that preventing trans-cis isomerisation effectively turns off internal conversion to the ground electronic state and enhances electron emission from the first electronically excited state.
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